Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
  • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
  • D21C9/153—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications with ozone
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C11/00—Regeneration of pulp liquors or effluent waste waters
  • D21C11/06—Treatment of pulp gases; Recovery of the heat content of the gases; Treatment of gases arising from various sources in pulp and paper mills; Regeneration of gaseous SO2, e.g. arising from liquors containing sulfur compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

• This invention relates generally to pulp bleaching and more particularly to a method for economically operating an ozone generator in connection with such pulp bleaching.
• ozone gas is generated on site either from air or from oxygen gas.
• ozone generator in a carrier gas of oxygen or air, depending upon the feed gas of the ozone generator.
• This mixture is fed to an ozone reactor in which it is brought into contact with wood pulp for bleaching the pulp.
• a high concentration of ozone in the carrier gas is desired in order to maintain a high reaction rate and to minimize the contact time required between the pulp and the ozone gas. Since ozone concentration from an ozone generator is directly controlled by oxygen concentration in the feed gas, it is clear that oxygen rich feed gas is desirable for the ozone generator.
• Such oxygen rich feed gas can be provided as essentially pure oxygen from distillation of air, or as oxygen enriched air resulting from adso ⁇ tion of nitrogen from air which is passed through a pressure swing adso ⁇ tion unit.
• relatively pure oxygen used as the feed gas for the ozone generator, usually only about four to seven percent ozone results. Therefore, a large fraction of the gas in an ozone/pulp contacting reactor consists of relatively pure oxygen carrier gas. After reaction with the pulp, this gas is discharged from the reactor as spent gas together with byproduct gases such as carbon monoxide, carbon dioxide, various hydrocarbon molecules, water vapor, and a minimal amount of residual ozone.
• the spent gas is usually passed through a hydrocarbon destructor and a gas dryer in order to return relatively pure gas to the ozone generator as feed gas.
• This process permits a gradual build-up of carbon dioxide in the system due to generation of carbon dioxide as a byproduct of the pulp/ozone reaction and as a result of catalytic oxidation of carbon monoxide and hydrocarbons in the hydrocarbon destructor.
• carbon dioxide is not harmful to the ozone/pulp reaction
• the accumulation of carbon dioxide in the recycled oxygen gas stream reduces the concentration of oxygen in the feed gas and, consequently, ozone concentration in the reagent gas being fed to the bleaching reactor. With each cycle through the system, the percentage of carbon dioxide increases, thereby increasing specific power consumption and further retarding the reaction.
• a part of the spent gas is purged from the gas loop so that, when replaced with pure oxygen or enriched air, the carbon dioxide content of the carrier gas can be maintained at an acceptable level.
• This level is usually determined based on the price of oxygen, electrical power cost, and required concentration of ozone. Purging of 10-20% of the gas volume is normally necessary to maintain the concentration of oxygen within the acceptable range.
• equilibrium oxygen concentration in the recycled spent gas is around 80-85%, when about 10% of the spent gas is purged, and cryogenically produced oxygen at virtually 100% purity is used as makeup oxygen.
• oxygen enriched air produced by a pressure swing adso ⁇ tion generator about 90-95% of the feed gas to the ozone generator is oxygen.
• the balance of the feed gas is nitrogen which has not been adsorbed and argon or other gases which are not adsorbable in the zeolite bed of the reactor.
• argon and other essentially inert gases also accumulate in the gas loop. This necessitates increased purging of gas from the system and a resulting increased demand for makeup gas.
• control is required in order to provide the proper level of purging and makeup gas additions.
• a single pass system is used, in which spent gas from the ozone pulp reactor is discarded or is reused for purposes unrelated to ozone generation. In any case, an economic cost is imposed on the operation.
• this is accomplished by providing a method for reusing spent gas from an ozone bleaching reactor in a pulp bleaching system having a pressure swing adso ⁇ tion device for supplying oxygen to an ozone generator including the steps of directing spent gas from a lint remover, which receives gas from the ozone bleaching reactor, after the gas is separated from the pulp, to a gas compressor, and compressing the spent gas; passing the compressed spent gas through a hydrocarbon destructor and cooler to oxidize any carbon monoxide and hydrocarbons and to cool the spent gas; passing the spent gas, together with injected compressed air, through a separator to remove mist; and passing the gas from the separator through the pressure swing adso ⁇ tion (PSA) device to separate nitrogen, carbon dioxide, and trace water vapor to produce air with an oxygen concentration greater than about 90% for ozone generator feed gas.
• PSA pressure swing adso ⁇ tion
• Figure 1 is a schematic flow chart representation of a spent gas recycling system according to the prior art
• Figure 2 is a schematic flow chart illustrating the spent gas recycling embodiment of the present invention.
• a conventional spent gas recycling system is charted in Figure 1.
• the pulp is discharged from the reactor through discharge line 120.
• the reaction gas including ozone, carrier gas, hydrocarbon gases, carbon dioxide, carbon monoxide, and mists and vapors is discharged from reactor 130 through gas discharge line 135 into lint remover 140. From lint remover 140, the gas travels through line 145 to gas compressor 150 in which it is compressed for discharge to hydrocarbon destructor and cooler 160, through compressed gas discharge line 155.
• oxygen from a liquid source is used for makeup oxygen to the feed gas of the ozone generator.
• pure oxygen is fed to the ozone generator, and an appropriate volume of purged gas is eliminated, a reasonably steady carbon dioxide level can be maintained. Nevertheless, a small but measurable quantity of pure oxygen is lost in the purged gas. Since pure oxygen is relatively expensive, this adds an economic cost burden to the process.
• Ozone reactor 130 discharges pulp through pulp discharge line 120 and spent bleaching gas through gas discharge line 135. After passing through lint remover 140, the spent gas is fed to gas compressor 150 through line 145. From compressor 150, compressed spent gas is fed to hydrocarbon destructor and cooler 160 through feed line 155. A portion of the compressed gas from line 155 is purged through purge line 255 to be used at another process such as oxygen delignification, for example.
• the gas now substantially free of mist, and augmented by the compressed air, enters PSA system 276 in which, after adso ⁇ tion of gas components on the zeolite of the system, enriched substantially dry air of approximately 90 to 95% oxygen is discharged through line 90 as feed gas for the ozone generator 100.
• Wood pulp is mixed with the ozone in its enriched air carrier gas from line 109, in inlet 115 of ozone reactor 130.
• Spent gas recycling through a pressure swing adso ⁇ tion system is also effective in removing undesirable carbon dioxide and moisture from the spent gas.
• Some gas purging will, however, still be required because of the gradual accumulation of argon in the system. Since argon is not adsorbed by zeolite, and since it does not participate in the bleaching reactions, the gas experiences a small increase in argon content with each cycle through the reactor system. A purge of approximately 10%, by volume, of spent gas for a 6% ozone concentration, yields optimum economic performance for the system. The impact of gas purging on the operating cost is relatively small since purged gas is replaced with air instead of pure oxygen.
• Another advantage of the method of the present invention is that it is possible to eliminate the hydrocarbon destructor system if the adsorbent of the pressure swing adso ⁇ tion system can effectively trap hydrocarbons and other gaseous reaction products generated in the ozone reactor. Freedom from carbon dioxide accumulation in the system resulting from adso ⁇ tion in the molecular sieve (zeolite) of the system, results in a high oxygen concentration in the spent gas. This permits effective usage of the spent gas for oxygen delignification, and it also results in a lower specific power consumption for the ozone generator when the oxygen rich spent gas is returned to the generator.
• the action of the pressure swing adso ⁇ tion unit depends upon the ability of zeolite or other molecular sieve material to selectively capture molecules from gases which pass through the system. As in any such system, it is necessary, periodically, to regenerate the molecular sieve by exposing it to an elevated temperature, a vacuum, or a combination of elevated temperature and vacuum.
• the pressure swing adso ⁇ tion process may be successfully applied when the required concentration of oxygen is not excessively high.
• the process is adequate; since, even though the argon contained in air is concentrated along with the oxygen of the air, other contaminants such as water vapor and carbon dioxide can be removed from the air together with nitrogen.
• argon accumulates in the system when the spent gas is recycled back to the pressure swing adso ⁇ tion unit in the present invention, a part of the spent gas will be purged in order to maintain the ozone generator feed gas within the acceptable range.
• carbon dioxide is no longer accumulating in the recycling system, the amount of gas purging required will be smaller.
• the purged spent gas be used for an oxygen delignification stage, if such is incorporated within the mill, or for combustion enhancement in a boiler.
• About 15% purging from the spent gas will meet the oxygen requirement for the oxygen delignification step if the oxygen appUcation is 2% on pulp and the ozone application is 1% on pulp at 6% ozone concentration.
• a purge of this magnitude will maintain the increase in argon concentration in the recycled gas system to an almost insignificant level.
• the equilibrium argon concentration in the ozone generator feed gas expected in the above example is less than about 10%.
• the oxygen concentration in the recycled gas system is maintained above 90% which is comparable to the oxygen concentration obtained by using only virgin air as pressure swing adso ⁇ tion feed gas.
• the expected oxygen concentration in the ozone generator feed gas in the conventional spent gas recycling method of the prior art is no more than 80-85% at an economically feasible purge rate.

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• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Paper (AREA)
• Separation Of Gases By Adsorption (AREA)
• Treating Waste Gases (AREA)
• Oxygen, Ozone, And Oxides In General (AREA)

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• 1994
  • 1994-03-22 BR BR9406030A patent/BR9406030A/pt not_active Application Discontinuation
  • 1994-03-22 CA CA002159444A patent/CA2159444A1/en not_active Abandoned
  • 1994-03-22 JP JP6522153A patent/JPH08510016A/ja active Pending
  • 1994-03-22 WO PCT/US1994/003100 patent/WO1994023123A1/en active IP Right Grant
  • 1994-03-22 AT AT94912840T patent/ATE187784T1/de active
  • 1994-03-22 DE DE69422167T patent/DE69422167T2/de not_active Expired - Fee Related
  • 1994-03-22 EP EP94912840A patent/EP0692044B1/de not_active Expired - Lifetime
• 1995
  • 1995-09-12 NO NO953594A patent/NO953594L/no not_active Application Discontinuation
  • 1995-09-26 FI FI954555A patent/FI954555A/fi unknown
• 1997
  • 1997-09-26 US US08/835,787 patent/US5944951A/en not_active Expired - Fee Related

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